CN113912981A - 一种高耐热性中Tg覆铜板及其制备方法 - Google Patents
一种高耐热性中Tg覆铜板及其制备方法 Download PDFInfo
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- CN113912981A CN113912981A CN202111299458.8A CN202111299458A CN113912981A CN 113912981 A CN113912981 A CN 113912981A CN 202111299458 A CN202111299458 A CN 202111299458A CN 113912981 A CN113912981 A CN 113912981A
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- parts
- epoxy resin
- copper
- resin
- novolac epoxy
- Prior art date
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- Pending
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 27
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 20
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 10
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 10
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Reinforced Plastic Materials (AREA)
Abstract
本发明公开了一种高耐热性中Tg覆铜板,具体涉及覆铜板技术领域,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,所述胶液包括以下原料:苯并恶嗪树脂、含磷环氧树脂、改性酚醛环氧树脂、双马来酰亚胺、无机填料、固化剂、固化催化剂、加工助剂和有机溶剂。本发明苯并恶嗪树脂优异的耐热性能和阻燃性能,与含磷环氧树脂复合使用不仅使得阻燃性能较好,而且力学性能得到改善,酚醛环氧树脂为高耐热性树脂,通过在酚醛环氧树脂中引入氟和磷,使得改性后的酚醛环氧树脂具有较好的热稳定性和较高的阻燃性。
Description
技术领域
本发明涉及覆铜板技术领域,更具体地说,本发明涉及一种高耐热性中Tg覆铜板及其制备方法。
背景技术
随着科学技术飞速发展,大规模工业集成化的形成,对人类自身居住环境造成无法弥补的损害,从而环境保护变得很迫切。近年来,电子技术飞速发展,电子产品对环境产生的影响日益严重,特别是电子垃圾产品,目前绝大部分电子产品采用卤素阻燃剂,卤素阻燃剂燃烧后,不但发烟量大,气味难闻,而且会产生腐蚀性很强的卤化氢气体。另据文献报道,含卤素的阻燃剂在高温裂解和燃烧时会产生二恶英,二苯并呋喃等致癌物质。因此开发无卤素阻燃的基板材料势在必行,已经成为业界的工业重点。另一方面,人类生活的安全性越来越广受社会的关注。为提高电子产品的安全可靠性,特别对于潮湿环境条件下使用的绝缘材料(如电机、电器等)安全可靠性,开发高绝缘性产品保证电子产品安全可靠性就是近年来的一个重要的发展方向。
覆铜板的构成部分:1、基板:高分子合成树脂和增强材料组成的绝缘层压板可以作为敷铜板的基板。合成树脂的种类繁多,常用的有酚醛树脂、环氧树脂、聚四氟乙烯等。增强材料一般有纸质和布质两种,它们决定了基板的机械性能,如耐浸焊性、抗弯强度等。2、铜箔:它是制造敷铜板的关键材料,必须有较高的导电率及良好的焊接性。要求铜箔表面不得有划痕、砂眼和皱褶,金属纯度不低于99.8%,厚度误差不大于±5um。按照部颁标准规定,铜箔厚度的标称系列为18、25、35、70和105um。我国目前正在逐步推广使用35um厚度的铜箔。铜箔越薄,越容易蚀刻和钻孔,特别适合于制造线路复杂的高密度的印制板。3、覆铜板粘合剂:粘合剂是铜箔能否牢固地覆在基板上的重要因素。敷铜板的抗剥强度主要取决于粘合剂的性能。
随着电子技术的飞速发展,对树脂覆铜板提出了更高、更严苛的要求。在覆铜板的生产过程中,可以通过合理添加填料达到或提高这些性能指标,满足客户一些特殊的要求。但是现有的覆铜板在使用过程中存在耐温效果较差,热应力和热分解温度较低,不能满足人们的使用需求。
发明内容
本发明的目的在于提供一种高耐热性中Tg覆铜板及其制备方法,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:一种高耐热性中Tg覆铜板,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,所述胶液包括以下重量份的原料:苯并恶嗪树脂80-120份、含磷环氧树脂60-80份、改性酚醛环氧树脂60-80份、双马来酰亚胺40-50份、无机填料30-40份、固化剂6-10份、固化催化剂0.5-5份、加工助剂5-10份和有机溶剂50-80份。
在一种优选的实施方式中,所述胶液包括以下重量份的原料:苯并恶嗪树脂90-110份、含磷环氧树脂65-75份、改性酚醛环氧树脂65-75份、双马来酰亚胺44-46份、无机填料33-37份、固化剂7-9份、固化催化剂2-3份、加工助剂7-8份和有机溶剂60-70份。
在一种优选的实施方式中,所述胶液包括以下重量份的原料:苯并恶嗪树脂100份、含磷环氧树脂70份、改性酚醛环氧树脂70份、双马来酰亚胺45份、无机填料35份、固化剂8份、固化催化剂2.5份、加工助剂7.5份和有机溶剂65份。
在一种优选的实施方式中,所述固化剂为双氰胺和邻苯二甲酸酐的混合物,且所述双氰胺和邻苯二甲酸酐的重量比为1:(2-5),所述固化催化剂为二甲基咪唑和邻苯二甲酸酐的混合物,所述二甲基咪唑和邻苯二甲酸酐的重量比为1:(5-8)。
在一种优选的实施方式中,所述无机填料为球形二氧化硅、氧化锌、氢氧化铝、改性硫酸钡、氮化硅和氮化硼中的两种或两种以上,所述加工助剂包括有硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂,所述硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂的重量比为1:(1.2-1.8):(1-1.5):(0.5-0.8),所述有机溶剂为二甲苯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚一种或两种以上混合。
一种高耐热性中Tg覆铜板的制备方法,具体制备步骤如下:
步骤一:改性酚醛环氧树脂的制备,称取酚醛环氧树脂超声搅拌分散于溶剂中,向分散液中加入二(3,3,3-三氟丙基)次磷酸钠和硅烷偶联剂,搅拌混合均匀后进行减压蒸馏去除溶剂,然后加热至80-120℃下反应2-4h,反应完成后得到改性酚醛环氧树脂备用;
步骤二:胶液的制备,将称取的苯并恶嗪树脂、含磷环氧树脂和步骤一中得到的改性酚醛环氧树脂熔融共混挤出造粒,得到混合改性树脂,向混合改性树脂中依次加入称取的有机溶剂、双马来酰亚胺、无机填料、固化剂、固化催化剂和加工助剂,循环搅拌2-6h调制形成胶液;
步骤三:半固化片的制备,将步骤二中得到的胶液通过垂直上胶机浸渍于电子级玻璃纤维布上,对浸渍有胶液的电子级玻璃纤维布进行干燥处理得到半固化片;
步骤四:根据实际需要选择适宜数量的半固化片叠放在一起,然后顶端和底端半固化片的表面各覆有一层铜箔,然后通过热压压合技术高耐热性中Tg覆铜板。
在一种优选的实施方式中,所述步骤一中二(3,3,3-三氟丙基)次磷酸钠加入量为酚醛环氧树脂分散液体积的5-15%。
在一种优选的实施方式中,所述步骤二中向混合改性树脂中加入有机溶剂后搅拌20-60min后再加入双马来酰亚胺,所述循环搅拌时搅拌速率为200-400转/分钟。
在一种优选的实施方式中,所述步骤三中干燥处理时干燥温度为120-150℃,干燥时间为15-25min。
在一种优选的实施方式中,所述步骤四中热压压合时的压力为1.5-3MPa,热压压合时的温度为200-240℃,热压压合的时间为45-60min。
本发明的技术效果和优点:
1、采用本发明的原料配方所制备出的高耐热性中Tg覆铜板,采用苯并恶嗪树脂、含磷环氧树脂和改性酚醛环氧树脂作为主要原料制备胶液,苯并恶嗪树脂优异的耐热性能和阻燃性能,与含磷环氧树脂复合使用不仅使得阻燃性能较好,而且力学性能得到改善,酚醛环氧树脂为高耐热性树脂,通过在酚醛环氧树脂中引入氟和磷,使得改性后的酚醛环氧树脂具有较好的热稳定性和较高的阻燃性,通过在苯并恶嗪树脂和含磷环氧树脂中加入改性酚醛环氧树脂能够降低使用含磷环氧树脂造成耐热性不足的影响,从而使得板材的耐热性和阻燃性较好;
2、本发明通过添加有双马来酰亚胺和无机填料,双马来酰亚胺为热稳定性高和力学性能较好的聚酰亚胺类树脂,双马来酰亚胺能够有效提高苯并恶嗪树脂、含磷环氧树脂和改性酚醛环氧树脂等混合改性树脂的交联密度,能够提高板材的力学性能,而无机填料能够提高覆铜基板的玻璃化转变温度,使得覆铜板的耐热冲击效果和剥离强度显著提高。
具体实施方式
下面将结合本发明中的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:
本发明提供了一种高耐热性中Tg覆铜板,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,所述胶液包括以下重量份的原料:苯并恶嗪树脂80份、含磷环氧树脂60份、改性酚醛环氧树脂60份、双马来酰亚胺40份、无机填料30份、固化剂6份、固化催化剂0.5份、加工助剂5份和有机溶剂50份。
在一种优选的实施方式中,所述固化剂为双氰胺和邻苯二甲酸酐的混合物,且所述双氰胺和邻苯二甲酸酐的重量比为1:3,所述固化催化剂为二甲基咪唑和邻苯二甲酸酐的混合物,所述二甲基咪唑和邻苯二甲酸酐的重量比为1:7。
在一种优选的实施方式中,所述无机填料为球形二氧化硅、氧化锌、氢氧化铝、改性硫酸钡、氮化硅和氮化硼中的两种或两种以上,所述加工助剂包括有硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂,所述硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂的重量比为1:1.5:1.2:0.6,所述有机溶剂为二甲苯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚一种或两种以上混合。
一种高耐热性中Tg覆铜板的制备方法,具体制备步骤如下:
步骤一:改性酚醛环氧树脂的制备,称取酚醛环氧树脂超声搅拌分散于溶剂中,向分散液中加入二(3,3,3-三氟丙基)次磷酸钠和硅烷偶联剂,搅拌混合均匀后进行减压蒸馏去除溶剂,然后加热至100℃下反应3h,反应完成后得到改性酚醛环氧树脂备用;
步骤二:胶液的制备,将称取的苯并恶嗪树脂、含磷环氧树脂和步骤一中得到的改性酚醛环氧树脂熔融共混挤出造粒,得到混合改性树脂,向混合改性树脂中依次加入称取的有机溶剂、双马来酰亚胺、无机填料、固化剂、固化催化剂和加工助剂,循环搅拌4h调制形成胶液;
步骤三:半固化片的制备,将步骤二中得到的胶液通过垂直上胶机浸渍于电子级玻璃纤维布上,对浸渍有胶液的电子级玻璃纤维布进行干燥处理得到半固化片;
步骤四:根据实际需要选择适宜数量的半固化片叠放在一起,然后顶端和底端半固化片的表面各覆有一层铜箔,然后通过热压压合技术高耐热性中Tg覆铜板。
在一种优选的实施方式中,所述步骤一中二(3,3,3-三氟丙基)次磷酸钠加入量为酚醛环氧树脂分散液体积的10%。
在一种优选的实施方式中,所述步骤二中向混合改性树脂中加入有机溶剂后搅拌50min后再加入双马来酰亚胺,所述循环搅拌时搅拌速率为300转/分钟。
在一种优选的实施方式中,所述步骤三中干燥处理时干燥温度为140℃,干燥时间为20min。
在一种优选的实施方式中,所述步骤四中热压压合时的压力为2.5MPa,热压压合时的温度为220℃,热压压合的时间为50min。
实施例2:
本发明提供了一种高耐热性中Tg覆铜板,所述胶液包括以下重量份的原料:苯并恶嗪树脂100份、含磷环氧树脂70份、改性酚醛环氧树脂70份、双马来酰亚胺45份、无机填料35份、固化剂8份、固化催化剂2.5份、加工助剂7.5份和有机溶剂65份。
实施例3:
与实施例1和2不同的是,本发明提供了一种高耐热性中Tg覆铜板,所述胶液包括以下重量份的原料:苯并恶嗪树脂120份、含磷环氧树脂80份、改性酚醛环氧树脂80份、双马来酰亚胺50份、无机填料40份、固化剂10份、固化催化剂5份、加工助剂10份和有机溶剂80份。
实施例4:
本发明提供了一种高耐热性中Tg覆铜板,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,所述胶液包括以下重量份的原料:苯并恶嗪树脂80份、含磷环氧树脂60份、酚醛环氧树脂60份、双马来酰亚胺40份、无机填料30份、固化剂6份、固化催化剂0.5份、加工助剂5份和有机溶剂50份。
在一种优选的实施方式中,所述固化剂为双氰胺和邻苯二甲酸酐的混合物,且所述双氰胺和邻苯二甲酸酐的重量比为1:3,所述固化催化剂为二甲基咪唑和邻苯二甲酸酐的混合物,所述二甲基咪唑和邻苯二甲酸酐的重量比为1:7。
在一种优选的实施方式中,所述无机填料为球形二氧化硅、氧化锌、氢氧化铝、改性硫酸钡、氮化硅和氮化硼中的两种或两种以上,所述加工助剂包括有硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂,所述硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂的重量比为1:1.5:1.2:0.6,所述有机溶剂为二甲苯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚一种或两种以上混合。
一种高耐热性中Tg覆铜板的制备方法,具体制备步骤如下:
步骤一:胶液的制备,将称取的苯并恶嗪树脂、含磷环氧树脂和酚醛环氧树脂熔融共混挤出造粒,得到混合改性树脂,向混合改性树脂中依次加入称取的有机溶剂、双马来酰亚胺、无机填料、固化剂、固化催化剂和加工助剂,循环搅拌4h调制形成胶液;
步骤二:半固化片的制备,将步骤一中得到的胶液通过垂直上胶机浸渍于电子级玻璃纤维布上,对浸渍有胶液的电子级玻璃纤维布进行干燥处理得到半固化片;
步骤三:根据实际需要选择适宜数量的半固化片叠放在一起,然后顶端和底端半固化片的表面各覆有一层铜箔,然后通过热压压合技术高耐热性中Tg覆铜板。
在一种优选的实施方式中,所述步骤一中向混合改性树脂中加入有机溶剂后搅拌50min后再加入双马来酰亚胺,所述循环搅拌时搅拌速率为300转/分钟。
在一种优选的实施方式中,所述步骤二中干燥处理时干燥温度为140℃,干燥时间为20min。
在一种优选的实施方式中,所述步骤三中热压压合时的压力为2.5MPa,热压压合时的温度为220℃,热压压合的时间为50min。
实施例5:
本发明提供了一种高耐热性中Tg覆铜板,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,所述胶液包括以下重量份的原料:苯并恶嗪树脂80份、含磷环氧树脂60份、改性酚醛环氧树脂60份、无机填料30份、固化剂6份、固化催化剂0.5份、加工助剂5份和有机溶剂50份。
在一种优选的实施方式中,所述固化剂为双氰胺和邻苯二甲酸酐的混合物,且所述双氰胺和邻苯二甲酸酐的重量比为1:3,所述固化催化剂为二甲基咪唑和邻苯二甲酸酐的混合物,所述二甲基咪唑和邻苯二甲酸酐的重量比为1:7。
在一种优选的实施方式中,所述无机填料为球形二氧化硅、氧化锌、氢氧化铝、改性硫酸钡、氮化硅和氮化硼中的两种或两种以上,所述加工助剂包括有硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂,所述硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂的重量比为1:1.5:1.2:0.6,所述有机溶剂为二甲苯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚一种或两种以上混合。
一种高耐热性中Tg覆铜板的制备方法,具体制备步骤如下:
步骤一:改性酚醛环氧树脂的制备,称取酚醛环氧树脂超声搅拌分散于溶剂中,向分散液中加入二(3,3,3-三氟丙基)次磷酸钠和硅烷偶联剂,搅拌混合均匀后进行减压蒸馏去除溶剂,然后加热至100℃下反应3h,反应完成后得到改性酚醛环氧树脂备用;
步骤二:胶液的制备,将称取的苯并恶嗪树脂、含磷环氧树脂和步骤一中得到的改性酚醛环氧树脂熔融共混挤出造粒,得到混合改性树脂,向混合改性树脂中依次加入称取的有机溶剂、无机填料、固化剂、固化催化剂和加工助剂,循环搅拌4h调制形成胶液;
步骤三:半固化片的制备,将步骤二中得到的胶液通过垂直上胶机浸渍于电子级玻璃纤维布上,对浸渍有胶液的电子级玻璃纤维布进行干燥处理得到半固化片;
步骤四:根据实际需要选择适宜数量的半固化片叠放在一起,然后顶端和底端半固化片的表面各覆有一层铜箔,然后通过热压压合技术高耐热性中Tg覆铜板。
在一种优选的实施方式中,所述步骤一中二(3,3,3-三氟丙基)次磷酸钠加入量为酚醛环氧树脂分散液体积的10%。
在一种优选的实施方式中,所述步骤二中向混合改性树脂中加入有机溶剂后搅拌50min后再加入双马来酰亚胺,所述循环搅拌时搅拌速率为300转/分钟。
在一种优选的实施方式中,所述步骤三中干燥处理时干燥温度为140℃,干燥时间为20min。
在一种优选的实施方式中,所述步骤四中热压压合时的压力为2.5MPa,热压压合时的温度为220℃,热压压合的时间为50min。
取上述实施例1-5所制得的覆铜板分别作为实验组1、实验组2、实验组3、实验组4和实验组5,并选取市售的中Tg覆铜基板作为对照组,对选取的覆铜板进行玻璃化温度、阻燃性(UL94)、热变形温度、热应力、热分解温度和剥离强度检测。测试结果如表一:
表一
由表一可知,本发明生产的覆铜板玻璃转化温度、阻燃性、热变形温度、热应力和热分解温度均高于市售的中Tg覆铜板,而且剥离强度较好,实施例4采用未改性的酚醛环氧树脂作为材料,与实施例1相比,剥离强度、玻璃转化温度、阻燃性、热变形温度、热应力和热分解温度略微降低,实施例5未添加双马来酰亚胺,剥离强度明显降低;采用苯并恶嗪树脂、含磷环氧树脂和改性酚醛环氧树脂作为主要原料制备胶液,苯并恶嗪树脂优异的耐热性能和阻燃性能,与含磷环氧树脂复合使用不仅使得阻燃性能较好,而且力学性能得到改善,酚醛环氧树脂为高耐热性树脂,通过在酚醛环氧树脂中引入氟和磷,使得改性后的酚醛环氧树脂具有较好的热稳定性和较高的阻燃性,通过在苯并恶嗪树脂和含磷环氧树脂中加入改性酚醛环氧树脂能够降低使用含磷环氧树脂造成耐热性不足的影响,从而使得板材的耐热性和阻燃性较好,双马来酰亚胺为热稳定性高和力学性能较好的聚酰亚胺类树脂,双马来酰亚胺能够有效提高苯并恶嗪树脂、含磷环氧树脂和改性酚醛环氧树脂等混合改性树脂的交联密度,能够提高板材的力学性能。
最后:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种高耐热性中Tg覆铜板,包括固化片层和铜箔层,所述固化片层通过多个半固化片堆叠而成,所述半固化片采用电子级玻璃布和胶液组成,其特征在于:所述胶液包括以下重量份的原料:苯并恶嗪树脂80-120份、含磷环氧树脂60-80份、改性酚醛环氧树脂60-80份、双马来酰亚胺40-50份、无机填料30-40份、固化剂6-10份、固化催化剂0.5-5份、加工助剂5-10份和有机溶剂50-80份。
2.根据权利要求1所述的一种高耐热性中Tg覆铜板,其特征在于:所述胶液包括以下重量份的原料:苯并恶嗪树脂90-110份、含磷环氧树脂65-75份、改性酚醛环氧树脂65-75份、双马来酰亚胺44-46份、无机填料33-37份、固化剂7-9份、固化催化剂2-3份、加工助剂7-8份和有机溶剂60-70份。
3.根据权利要求1所述的一种高耐热性中Tg覆铜板,其特征在于:所述胶液包括以下重量份的原料:苯并恶嗪树脂100份、含磷环氧树脂70份、改性酚醛环氧树脂70份、双马来酰亚胺45份、无机填料35份、固化剂8份、固化催化剂2.5份、加工助剂7.5份和有机溶剂65份。
4.根据权利要求1所述的一种高耐热性中Tg覆铜板,其特征在于:所述固化剂为双氰胺和邻苯二甲酸酐的混合物,且所述双氰胺和邻苯二甲酸酐的重量比为1:(2-5),所述固化催化剂为二甲基咪唑和邻苯二甲酸酐的混合物,所述二甲基咪唑和邻苯二甲酸酐的重量比为1:(5-8)。
5.根据权利要求1所述的一种高耐热性中Tg覆铜板,其特征在于:所述无机填料为球形二氧化硅、氧化锌、氢氧化铝、改性硫酸钡、氮化硅和氮化硼中的两种或两种以上,所述加工助剂包括有硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂,所述硅烷偶联剂、2-甲基咪唑、2-苯基咪唑和抗氧剂的重量比为1:(1.2-1.8):(1-1.5):(0.5-0.8),所述有机溶剂为二甲苯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚一种或两种以上混合。
6.一种高耐热性中Tg覆铜板的制备方法,其特征在于:具体制备步骤如下:
步骤一:改性酚醛环氧树脂的制备,称取酚醛环氧树脂超声搅拌分散于溶剂中,向分散液中加入二(3,3,3-三氟丙基)次磷酸钠和硅烷偶联剂,搅拌混合均匀后进行减压蒸馏去除溶剂,然后加热至80-120℃下反应2-4h,反应完成后得到改性酚醛环氧树脂备用;
步骤二:胶液的制备,将称取的苯并恶嗪树脂、含磷环氧树脂和步骤一中得到的改性酚醛环氧树脂熔融共混挤出造粒,得到混合改性树脂,向混合改性树脂中依次加入称取的有机溶剂、双马来酰亚胺、无机填料、固化剂、固化催化剂和加工助剂,循环搅拌2-6h调制形成胶液;
步骤三:半固化片的制备,将步骤二中得到的胶液通过垂直上胶机浸渍于电子级玻璃纤维布上,对浸渍有胶液的电子级玻璃纤维布进行干燥处理得到半固化片;
步骤四:根据实际需要选择适宜数量的半固化片叠放在一起,然后顶端和底端半固化片的表面各覆有一层铜箔,然后通过热压压合技术高耐热性中Tg覆铜板。
7.根据权利要求6所述的一种高耐热性中Tg覆铜板的制备方法,其特征在于:所述步骤一中二(3,3,3-三氟丙基)次磷酸钠加入量为酚醛环氧树脂分散液体积的5-15%。
8.根据权利要求6所述的一种高耐热性中Tg覆铜板的制备方法,其特征在于:所述步骤二中向混合改性树脂中加入有机溶剂后搅拌20-60min后再加入双马来酰亚胺,所述循环搅拌时搅拌速率为200-400转/分钟。
9.根据权利要求6所述的一种高耐热性中Tg覆铜板的制备方法,其特征在于:所述步骤三中干燥处理时干燥温度为120-150℃,干燥时间为15-25min。
10.根据权利要求6所述的一种高耐热性中Tg覆铜板的制备方法,其特征在于:所述步骤四中热压压合时的压力为1.5-3MPa,热压压合时的温度为200-240℃,热压压合的时间为45-60min。
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